CN112575346A - Super-stable electrocatalyst material for efficient acidic oxygen evolution reaction and preparation method thereof - Google Patents

Super-stable electrocatalyst material for efficient acidic oxygen evolution reaction and preparation method thereof Download PDF

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CN112575346A
CN112575346A CN202011367292.4A CN202011367292A CN112575346A CN 112575346 A CN112575346 A CN 112575346A CN 202011367292 A CN202011367292 A CN 202011367292A CN 112575346 A CN112575346 A CN 112575346A
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CN112575346B (en
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李睿
胡飞
熊宇杰
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China Hydrogen Energy Technology Guangdong Co ltd
Xinyu Jintong Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C16/00—Alloys based on zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses an ultra-stable electrocatalyst material for efficient acidic oxygen evolution reaction, which is a (W, Mo, Nb, Ta, Zr, Hf, Re, Os) -Ir- (B, P) block alloy material, and the specific components of the alloy are (W, Mo, Nb, Ta, Zr, Hf, Re, Os) x-Iry- (B, P) z, x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 10 and less than or equal to 20, z is more than or equal to 0 and less than or equal to 20, wherein x, y and z are atomic percent of elements. The invention also discloses a preparation method of the ultra-stable electrocatalyst material for the efficient acidic oxygen evolution reaction. The material has excellent electro-catalytic activity of acid OER and ultrahigh stability, can be used as an anode of an industrial acid water electrolysis hydrogen production device, is simple in preparation method and easy to operate, and is beneficial to large-scale application of PEM water electrolysis technology.

Description

Super-stable electrocatalyst material for efficient acidic oxygen evolution reaction and preparation method thereof
Technical Field
The invention relates to an electrocatalyst material and a preparation method thereof, belongs to the application field of the electrocatalyst material, and particularly relates to an ultrastable electrocatalyst material for efficient acidic oxygen evolution reaction and a preparation method thereof.
Background
With the aggravation of the world energy crisis, the development of new energy is urgent, and the electrocatalytic energy conversion technology, such as electrocatalytic decomposition of water for hydrogen production, electrocatalytic carbon dioxide reduction, electrocatalytic nitrogen reduction and the like, is an important way for replacing fossil energy, reducing carbon emission and obtaining renewable fuel. Among them, the electrochemical oxygen evolution reaction is an important anode half-reaction in the electrocatalytic energy conversion process. However, electrochemical oxygen evolution reactions are kinetically slow and require highly efficient catalysts to lower the reaction energy barrier and thus accelerate the oxygen evolution reaction.
In recent years, a large number of high-efficiency and stable alkaline oxygen evolution reaction electrocatalyst materials have been developed, however, the lack of high-activity and stable oxygen evolution reaction electrocatalyst under acidic conditions greatly hinders the wide commercialization of acidic electrolyzed water, and especially, the development of high-efficiency and stable acidic oxygen evolution reaction electrocatalyst is important in consideration of the advantages of higher mass transfer rate, product purity, efficiency and the like of electrocatalytic reaction in an acidic pem (proton exchange membrane) electrolytic cell.
The Ir material is considered to be the electrocatalyst with the best oxygen evolution reaction under the acidic condition, and related research work at present mainly focuses on Ir-based or Ir-oxide-based nano-structure materials, however, most of the catalyst materials are synthesized by a wet chemical method, and a surfactant adsorbed on a nano structure is difficult to remove, which may affect the activity of the catalyst, and meanwhile, the Ir-based nano-particle substances have poor stability under the high current density condition and cannot meet the requirements of industrial conditions, so that the development of the Ir-based acid oxygen evolution reaction electrocatalyst with higher stability has a long-term significance in the field of industrial acidic electrolyzed water.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the ultra-stable electrocatalyst material for the efficient acidic oxygen evolution reaction and the preparation method thereof, the material has excellent acidic OER electrocatalytic activity and ultrahigh stability, can be used as an anode of an industrial acidic water electrolysis hydrogen production device, and is simple in preparation method, easy to operate and beneficial to large-scale application of a PEM water electrolysis technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an ultra-stable electrocatalyst material for efficient acidic oxygen evolution reaction, wherein the electrocatalyst is a (W, Mo, Nb, Ta, Zr, Hf, Re, Os) -Ir- (B, P) block alloy material.
Further, the specific components of the alloy material are (W, Mo, Nb, Ta, Zr, Hf, Re, Os) x-Iry- (B, P) z, x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 10 and less than or equal to 20, z is more than or equal to 0 and less than or equal to 20, wherein x, y and z are atomic percent of elements.
Further, the electrocatalytic activity of the alloy material reaches 10mA/cm in an acidic medium with pH of 02The overpotential required for the catalytic current density is 270-425 mV.
Further, the electrocatalytic activity of the alloy material reaches 10mA/cm in an acidic medium with pH of 02The overpotential range required by the catalytic current density is 270-300 mV.
Further, the alloy material is 100mA/cm2The stable operation time under the current density condition is more than 800 hours, and the overpotential rising rate ranges from 2 to 5 muV/h.
The invention provides a preparation method of an ultra-stable electrocatalyst material for efficient acidic oxygen evolution reaction, wherein the electrocatalyst is a (W, Mo, Nb, Ta, Zr, Hf, Re, Os) -Ir- (B, P) block alloy material, the specific components of the alloy are (W, Mo, Nb, Ta, Zr, Hf, Re, Os) x-Iry- (B, P) z, x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 10 and less than or equal to 20, z is more than or equal to 0 and less than or equal to 20, wherein x, y and z are atomic percentages of elements, the material is directly cast and molded by adopting an electric arc melting technology, and the melting temperature is more than 3500 ℃.
Further, the method comprises the following steps:
(1) preparing a master alloy ingot: according to nominal components (W, Mo, Nb, Ta, Zr, Hf, Re, Os) x-Iry- (B, P) z of a master alloy, wherein x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 10 and less than or equal to 20, and z is more than or equal to 0 and less than or equal to 20, wherein x, y and z are atomic percent of elements, alloy raw materials (with purity of 98.0-99.9 wt%) are subjected to batching, then arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is 200-300A, and in order to ensure that the alloy components are uniform, the master alloy is repeatedly turned and melted in a furnace to obtain a master alloy;
(2) alloy casting and forming: and (2) remelting the uniform master alloy ingot in the step (1) through arc melting, infiltrating the molten alloy into a water-cooled copper mold through a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain the (W, Mo, Nb, Ta, Zr, Hf, Re, Os) -Ir- (B, P) electrocatalyst bar or plate with a certain shape and size.
Further, in the step (1), the master alloy is repeatedly turned and smelted in the furnace for four to ten times to obtain a master alloy ingot.
The invention provides a super-stable electrocatalyst material for efficient acidic oxygen evolution reaction, wherein the electrocatalyst is W60Ir20B20A bulk alloy material; where 60 and 20 are atomic percentages of the elements.
Further, the electrocatalytic activity of the alloy material reaches 10mA/cm in an acidic medium with pH of 02The overpotential range required by the catalytic current density is 270-300 mV; the alloy material is 100mA/cm2The stable operation time under the current density condition is more than 800 hours, and the overpotential rising rate ranges from 2 to 5 muV/h.
Further, the preparation method comprises the following steps:
(1) preparing a master alloy ingot: according to the nominal composition W of the master alloy60Ir20B20Wherein60 and 20 are atomic percentages of elements, alloy raw materials (with the purity of 98.0-99.9 wt%) are mixed, arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is 200-300A, and in order to ensure that the alloy components are uniform, the master alloy is repeatedly turned and melted in the furnace for four to ten times to obtain a master alloy ingot;
(2) alloy casting and forming: remelting the uniform master alloy ingot in the step (1) by arc melting, infiltrating the molten alloy into a water-cooled copper mold by a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain W with a certain shape and size60Ir20B20Electrocatalyst rods or plates.
Compared with the prior art, the invention has the following beneficial effects:
(1) the oxygen evolution reaction electrocatalyst prepared by the invention has ultrahigh stability under an acidic condition, and the problem of limitation of insufficient long-term service stability of the existing acidic oxygen evolution reaction electrocatalyst is solved.
(2) The method of electric arc melting is adopted for direct casting and molding, the preparation process is simple, complex chemical synthesis process is not needed, and the method is suitable for large-scale industrial production.
Drawings
FIG. 1 is W prepared in example 1 of the present invention60Ir20B20X-ray diffraction pattern of the electrocatalyst material rods.
FIG. 2 is W prepared in example 1 of the present invention60Ir20B20Scanning electron microscopy of a rod of electrocatalyst material.
FIG. 3 is W prepared in example 1 of the present invention60Ir20B20Electrocatalyst materials and commercial IrO2And linear sweep voltammograms of the Ir/C electrode.
FIG. 4 shows W prepared in example 1 of the present invention60Ir20B20Electrocatalyst materials and commercial IrO2And Ir/C electrode at 10mA/cm2Comparative plot of voltage versus time curves under current density conditions.
FIG. 5 shows the results of example 1 of the present inventionPreparation of the obtained W60Ir20B20The electrocatalyst material was at 100mA/cm2Voltage versus time plot under current density conditions.
Detailed Description
The acidic oxygen evolution reaction electrocatalyst provided by the invention is a (W, Mo, Nb, Ta, Zr, Hf, Re, Os) -Ir- (B, P) alloy block material, and the design characteristic of the alloy components is that a noble metal active element Ir is mixed with a high-melting-point metal element and a light nonmetal element. The specific components of the alloy are (W, Mo, Nb, Ta, Zr, Hf, Re, Os) x-Iry- (B, P) z, x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 10 and less than or equal to 20, and z is more than or equal to 0 and less than or equal to 20, wherein x, y and z are atomic percent of elements.
It can be directly used as anode material for oxygen evolution reaction, has excellent electrocatalytic activity, and reaches 10mA/cm in acid medium with pH 02The overpotential range required by the catalytic current density is 270-300 mV. It can also be used as acidic oxygen evolution electrocatalyst, and has ultrahigh stability of 100mA/cm2The stable operation time under the current density condition is more than 800 hours, and the overpotential rising rate ranges from 2 to 5 muV/h.
The invention will now be further described with reference to the accompanying drawings and specific embodiments.
Example 1
In this example, the nominal composition of the alloy selected is W60Ir20B20The electrocatalyst material was prepared as follows:
(1) preparing a master alloy ingot: according to the nominal composition W of the master alloy60Ir20B20Alloy raw materials W, Ir and B (with the purity of 98.0-99.9 wt%) are mixed, arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is 200A-300A, and in order to ensure the uniformity of alloy components, the master alloy is repeatedly turned and melted for four to ten times in a furnace to obtain a master alloy ingot.
(2) Alloy casting and forming: remelting the uniform master alloy ingot in the step (1) by arc melting, infiltrating the molten alloy into a water-cooled copper mold by a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain the diameterIs 2mm of W60Ir20B20An electrocatalyst rod.
And (3) effect testing:
characterization of the W obtained in this example by X-ray diffraction60Ir20B20The structure of the alloy bar, which gives the results shown in FIG. 1, has a two-phase structure, known from a comparison of PDF cards, WIr phase and W phase respectively2And (B) phase.
Shown in FIG. 2 is W60Ir20B20The scanning electron microscope picture of the alloy can also observe obvious two-phase separation micro-morphology.
The obtained alloy is subjected to acidic oxygen evolution reaction performance test, a three-electrode device is adopted for the test, and the W with a fixed exposed area60Ir20B20Alloy pattern (bare area 0.322 cm)2) As a working electrode, a counter electrode is a platinum wire electrode, a reference electrode is a standard Ag/AgCl electrode, an electrolyte is a 0.5mol/L sulfuric acid solution, and the scanning speed is 5 mV/s. For ease of comparison, commercial IrO was tested under the same conditions2And the acidic oxygen evolution reactivity of Ir/C. The linear voltammogram curves of different materials after conversion to standard hydrogen electrode potential, W, are shown in FIG. 360Ir20B20The alloy electrode material reaches 10mA/cm2The overpotential required for catalyzing current density is 291mV, which is obviously superior to commercial IrO2(302mV) and Ir/C (314mV) electrodes.
When the constant current test was performed on each electrode, the voltage-time curve was as shown in FIG. 4, and it was found that when the current density was 10mA/cm2W as prepared in example 160Ir20B20The alloy electrocatalyst electrode can stably operate in 0.5mol/L sulfuric acid electrolyte for more than 50 hours, and the commercial IrO under the same condition2And the Ir/C electrode can only be maintained for 4.6 hours and 10.5 hours, respectively, catalyst failure occurs.
FIG. 5 further shows W60Ir20B20The alloy electrocatalyst electrode has a current density of 100mA/cm2Voltage-time curves under the conditions, as can be seen from the figure, even at higher voltagesUnder the condition of current density, the electrode material still keeps high electrocatalytic activity after the super-long acidic oxygen evolution reaction, and the overpotential rising rate is lower than 4 muV/h within 800 hours. Demonstration of W prepared according to the invention60Ir20B20The alloy electrocatalyst has excellent stability of acidic oxygen evolution reaction.
Example 2
In this example, the nominal composition of the alloy selected is W80Ir10B10The electrocatalyst material was prepared as follows:
(1) preparing a master alloy ingot: according to the nominal composition W of the master alloy80Ir10B10Alloy raw materials W, Ir and B (with the purity of 98.0-99.9 wt%) are mixed, arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is more than 200A, and in order to ensure the uniformity of alloy components, the master alloy is repeatedly turned and melted for more than four times in a furnace to obtain a master alloy ingot.
(2) Alloy casting and forming: remelting the uniform master alloy ingot in the step (1) by arc melting, infiltrating the molten alloy into a water-cooled copper mold by a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain W with the diameter of 2mm80Ir10B10An electrocatalyst rod.
And (3) effect testing:
the catalyst rods were tested according to example 1, W80Ir10B10The alloy electrode material reaches 10mA/cm2The overpotential required for the catalytic current density is 381mV, and the stable operation in 0.5mol/L sulfuric acid electrolyte can be far more than 20 hours.
Example 3
In this example, Mo is the nominal component of the alloy60Ir20B20The electrocatalyst material was prepared as follows:
(1) preparing a master alloy ingot: according to the nominal composition Mo of master alloy60Ir20B20Mixing alloy raw materials W, Ir and B (with the purity of 98.0-99.9 wt%), and then carrying out high-purity Ar atmosphereAnd under protection, arc melting is carried out, the melting current is more than 200A, and in order to ensure that the alloy components are uniform, the master alloy is repeatedly turned and melted for more than four times in the furnace to obtain a master alloy ingot.
(2) Alloy casting and forming: remelting the uniform master alloy ingot in the step (1) by arc melting, infiltrating the molten alloy into a water-cooled copper mold by a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain Mo with the diameter of 2mm60Ir20B20An electrocatalyst rod.
And (3) effect testing:
the catalyst rods were tested as in example 1, Mo60Ir20B20The alloy electrode material reaches 10mA/cm2The overpotential required for the catalytic current density is 356mV, which enables stable operation in 0.5mol/L sulfuric acid electrolyte for more than 20 hours.
Example 4
In this example, the nominal alloy component selected is Nb60Ir20P20The electrocatalyst material was prepared as follows:
(1) preparing a master alloy ingot: nb according to the nominal composition of the master alloy60Ir20P20Alloy raw materials W, Ir and B (with the purity of 98.0-99.9 wt%) are mixed, arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is more than 200A, and in order to ensure the uniformity of alloy components, the master alloy is repeatedly turned and melted for more than four times in a furnace to obtain a master alloy ingot.
(2) Alloy casting and forming: remelting the uniform master alloy ingot in the step (1) by arc melting, infiltrating the molten alloy into a water-cooled copper mold by a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain Nb with the diameter of 2mm60Ir20P20An electrocatalyst rod.
And (3) effect testing:
the catalyst rods were tested as in example 1, Nb60Ir20B20The alloy electrode material reaches 10mA/cm2Excess required to catalyze current densityThe potential is 324mV, and the stable operation in 0.5mol/L sulfuric acid electrolyte can be greatly exceeded for 50 hours.
Example 5
In this example, Ta is the nominal component of the alloy selected60Ir20B20The electrocatalyst material was prepared as follows:
(1) preparing a master alloy ingot: according to the nominal composition Ta of the master alloy60Ir20B20Alloy raw materials W, Ir and B (with the purity of 98.0-99.9 wt%) are mixed, arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is more than 200A, and in order to ensure the uniformity of alloy components, the master alloy is repeatedly turned and melted for more than four times in a furnace to obtain a master alloy ingot.
(2) Alloy casting and forming: remelting the uniform master alloy ingot in the step (1) by arc melting, infiltrating the molten alloy into a water-cooled copper mold by a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain Ta with the diameter of 2mm60Ir20B20An electrocatalyst rod.
And (3) effect testing:
the catalyst rods were tested as in example 1, Ta60Ir20B20The alloy electrode material reaches 10mA/cm2The overpotential required for the catalytic current density is 312mV, which enables stable operation in a 0.5mol/L sulfuric acid electrolyte for well over 50 hours.
Example 6
In this example, Zr is the nominal component of the alloy selected for use60Ir20B20The electrocatalyst material was prepared as follows:
(1) preparing a master alloy ingot: zr according to the nominal composition of the master alloy60Ir20B20Alloy raw materials W, Ir and B (with the purity of 98.0-99.9 wt%) are mixed, arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is more than 200A, and in order to ensure the uniformity of alloy components, the master alloy is repeatedly turned and melted for more than four times in a furnace to obtain a master alloy ingot.
(2) Alloy casting and forming: remelting the uniform master alloy ingot obtained in the step (1) by arc melting, infiltrating the molten alloy into a water-cooled copper mold by a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain Zr with the diameter of 2mm60Ir20B20An electrocatalyst rod.
And (3) effect testing:
the catalyst rods were tested as in example 1, Zr60Ir20B20The alloy electrode material reaches 10mA/cm2The overpotential required for the catalytic current density is 395mV, which enables stable operation in 0.5mol/L sulfuric acid electrolyte for well over 50 hours.
Example 7
In this example, the nominal composition of the alloy selected is Hf60Ir20P20The electrocatalyst material was prepared as follows:
(1) preparing a master alloy ingot: according to the nominal composition Hf of the master alloy60Ir20P20Alloy raw materials W, Ir and B (with the purity of 98.0-99.9 wt%) are mixed, arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is more than 200A, and in order to ensure the uniformity of alloy components, the master alloy is repeatedly turned and melted for more than four times in a furnace to obtain a master alloy ingot.
(2) Alloy casting and forming: remelting the uniform master alloy ingot in the step (1) by arc melting, infiltrating the molten alloy into a water-cooled copper mold by a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain Hf with the diameter of 2mm60Ir20P20An electrocatalyst rod.
And (3) effect testing:
the catalyst rods were tested as in example 1, Hf60Ir20P20The alloy electrode material reaches 10mA/cm2The overpotential required for the catalytic current density is 340mV, which can stably operate in 0.5mol/L sulfuric acid electrolyte for more than 50 hours.
Example 8
In this example, the nominal composition of the alloy selected is Re60Ir20P20The electrocatalyst material was prepared as follows:
(1) preparing a master alloy ingot: according to the nominal composition Re of the master alloy60Ir20P20Alloy raw materials W, Ir and B (with the purity of 98.0-99.9 wt%) are mixed, arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is more than 200A, and in order to ensure the uniformity of alloy components, the master alloy is repeatedly turned and melted for more than four times in a furnace to obtain a master alloy ingot.
(2) Alloy casting and forming: remelting the uniform master alloy ingot in the step (1) by arc melting, infiltrating the molten alloy into a water-cooled copper mold by a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain Re with the diameter of 2mm60Ir20P20An electrocatalyst rod.
And (3) effect testing:
the catalyst rods were tested as in example 1, Re60Ir20P20The alloy electrode material reaches 10mA/cm2The overpotential required for the catalytic current density is 421mV, which can stably operate in 0.5mol/L sulfuric acid electrolyte for more than 10 hours.
Example 9
In this example, the nominal composition of the alloy we chose is Os60Ir20B20The electrocatalyst material was prepared as follows:
(1) preparing a master alloy ingot: according to the nominal composition Os of the master alloy60Ir20B20Alloy raw materials W, Ir and B (with the purity of 98.0-99.9 wt%) are mixed, arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is more than 200A, and in order to ensure the uniformity of alloy components, the master alloy is repeatedly turned and melted for more than four times in a furnace to obtain a master alloy ingot.
(2) Alloy casting and forming: remelting the uniform master alloy ingot in the step (1) by arc melting, and infiltrating the molten alloy into a water-cooled copper mould by a negative pressure suction casting methodThe alloy melt was cooled in a copper mold to obtain Os of 2mm diameter60Ir20B20An electrocatalyst rod.
And (3) effect testing:
the catalyst rods were tested according to example 1, Os60Ir20B20The alloy electrode material reaches 10mA/cm2The overpotential required for the catalytic current density is 286mV, which enables stable operation in 0.5mol/L sulfuric acid electrolyte for well over 50 hours.
In other examples, (W, Mo, Nb, Ta, Zr, Hf, Re, Os) -Ir- (B, P) series electrocatalyst can be prepared according to the same method of the embodiment, and bars or plates with different components can be obtained by only changing the nominal components of raw material ingredients.
The present invention is not limited to the above-described embodiments, and various changes and modifications of the present invention are intended to be included within the scope of the claims and the equivalent technology of the present invention if they do not depart from the spirit and scope of the present invention.

Claims (10)

1. An ultra-stable electrocatalyst material for efficient acidic oxygen evolution reactions, characterized by: the electrocatalyst is a (W, Mo, Nb, Ta, Zr, Hf, Re, Os) -Ir- (B, P) block alloy material.
2. An electrocatalyst material according to claim 1, wherein: the specific components of the alloy material are (W, Mo, Nb, Ta, Zr, Hf, Re, Os) x-Iry- (B, P) z, x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 10 and less than or equal to 20, z is more than or equal to 0 and less than or equal to 20, wherein x, y and z are atomic percent of elements.
3. An electrocatalyst material according to claim 1, wherein: the electrocatalytic activity of the alloy material reaches 10mA/cm in an acid medium with pH of 02The overpotential required for the catalytic current density is 270-425 mV.
4. An electrocatalyst material according to claim 1, wherein: the alloy material is 100mA/cm2The stable operation time under the current density condition is more than 800 hours, and the overpotential rising rate ranges from 2 to 5 muV/h.
5. A preparation method of an ultra-stable electrocatalyst material for efficient acidic oxygen evolution reaction is characterized by comprising the following steps: the electrocatalyst is a (W, Mo, Nb, Ta, Zr, Hf, Re, Os) -Ir- (B, P) block alloy material, the specific components of the alloy are (W, Mo, Nb, Ta, Zr, Hf, Re, Os) x-Iry- (B, P) z, x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 10 and less than or equal to 20, z is more than or equal to 0 and less than or equal to 20, wherein x, y and z are atomic percentages of elements, the electrocatalyst is directly cast and molded by adopting an electric arc melting technology, and the melting temperature is more than 3500 ℃.
6. The method of claim 5, comprising the steps of:
(1) preparing a master alloy ingot: according to nominal components (W, Mo, Nb, Ta, Zr, Hf, Re, Os) x-Iry- (B, P) z of a master alloy, wherein x is more than or equal to 60 and less than or equal to 80, y is more than or equal to 10 and less than or equal to 20, and z is more than or equal to 0 and less than or equal to 20, wherein x, y and z are atomic percent of elements, alloy raw materials (with purity of 98.0-99.9 wt%) are subjected to batching, then arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is 200-300A, and in order to ensure that the alloy components are uniform, the master alloy is repeatedly turned and melted in a furnace to obtain a master alloy;
(2) alloy casting and forming: and (2) remelting the uniform master alloy ingot in the step (1) through arc melting, infiltrating the molten alloy into a water-cooled copper mold through a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain the (W, Mo, Nb, Ta, Zr, Hf, Re, Os) -Ir- (B, P) electrocatalyst bar or plate.
7. The method of claim 6, wherein: in the step (1), the master alloy is repeatedly turned and smelted for four to ten times in the furnace to obtain a master alloy ingot.
8. An ultra-stable electrocatalyst material for efficient acidic oxygen evolution reactions, characterized by: the electrocatalyst is W60Ir20B20A bulk alloy material; where 60 and 20 are atomic percentages of the elements.
9. An electrocatalyst material according to claim 8, wherein: the electrocatalytic activity of the alloy material reaches 10mA/cm in an acid medium with pH of 02The overpotential range required by the catalytic current density is 270-300 mV; the alloy material is 100mA/cm2The stable operation time under the current density condition is more than 800 hours, and the overpotential rising rate ranges from 2 to 5 muV/h.
10. Electrocatalyst material according to claim 8, characterized in that the preparation method comprises the steps of:
(1) preparing a master alloy ingot: according to the nominal composition W of the master alloy60Ir20B2060 and 20 are atomic percentages of elements, alloy raw materials (with the purity of 98.0-99.9 wt%) are mixed, arc melting is carried out under the protection of high-purity Ar atmosphere, the melting current is 200-300A, and in order to ensure that the alloy components are uniform, the master alloy is repeatedly turned and melted in a furnace to obtain a master alloy ingot;
(2) alloy casting and forming: remelting the uniform master alloy ingot in the step (1) by arc melting, infiltrating the molten alloy into a water-cooled copper mold by a negative pressure suction casting method, and cooling the alloy melt in the copper mold to obtain W60Ir20B20Electrocatalyst rods or plates.
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